EP3733742B1

EP3733742B1 - Manufacturing method for low molecular weight polytetrafluoroethylene, and powder

Info

Publication number: EP3733742B1
Application number: EP19751304.7A
Authority: EP
Inventors: Masayuki Tsuji; Hirotoshi Yoshida
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2018-02-07
Filing date: 2019-02-05
Publication date: 2023-01-25
Anticipated expiration: 2039-02-05
Also published as: US11028239B2; JP2019137851A; WO2019156053A1; EP3733742A1; CN111630087B; JP6590096B2; US20210009769A1; EP3733742A4; CN111630087A

Description

TECHNICAL FIELD

The disclosure relates to methods for producing low molecular weight polytetrafluoroethylene, and powder.

BACKGROUND ART

Low molecular weight polytetrafluoroethylene (also referred to as "polytetrafluoroethylene wax" or "polytetrafluoroethylene micro powder") having a molecular weight of several thousands to several hundreds of thousands has excellent chemical stability and a very low surface energy, as well as low fibrillatability. Thus, low molecular weight polytetrafluoroethylene is used as an additive for improving the smoothness and the texture of film surfaces in production of articles such as plastics, inks, cosmetics, coatings, and greases (for example, see Patent Literature 1).
Examples of known methods for producing low molecular weight polytetrafluoroethylene include polymerization, radiolysis, and pyrolysis. In the radiolysis, conventionally, it has been common that high molecular weight polytetrafluoroethylene is irradiated in the air atmosphere to provide low molecular weight polytetrafluoroethylene.
Patent Literature 2 describes a method of pulverizing a polytetrafluoroethylene resin or other degradable polymers by utilizing the decay action of radiation. The document mentions various oxygen concentrations during irradiation, such as 21%, 60% and 100%. According to the document, average particle size decreases as the irradiation dose increases, and the average particle size decreases by increasing the oxygen concentration in the irradiation atmosphere gas.^
Patent Literature 3 describes a method for producing a sliding member including a resinous material that includes a fluororesin. It is desired to be provide a crosslinked fluororesin material to improve wear, and to this end e.g. PTFE is irradiated at a temperature above its melting temperature in an inert gas atmosphere containing not more than 1.33 kPa of oxygen.
Lunkwitz K et al reviewed the modification of perfluorinated polymers by high energy irradiation and the role of oxygen therein in Journal of Fluorine Chemistry 125 (2004), pages 863-873.

CITATION LIST

- Patent Literature

Patent Literature 1: JP H10-147617 A
Patent Literature 2: JP H04-91134
Patent Literature 3: US 2004/0082701 A1

SUMMARY OF INVENTION

- Technical Problem

The disclosure aims to provide a method for producing low molecular weight polytetrafluoroethylene less likely to generate C6-C14 perfluorocarboxylic acids and salts thereof.

- Solution to problem

The disclosure relates to a method for producing low molecular weight polytetrafluoroethylene, including: (1) feeding high molecular weight polytetrafluoroethylene having a standard specific gravity of 2.130-2.230, determined in conformity with ASTM D4895; and a gas mixture containing an inert gas and oxygen and having an oxygen content relative to the total of the inert gas and oxygen of 1 to 5 vol% into an airtight container; and (2) irradiating the high molecular weight polytetrafluoroethylene with a radiation selected from electron beams, gamma rays, X-rays, and neutron beams to provide low molecular weight polytetrafluoroethylene having a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s; wherein the melt viscosity is a value determined by heating a 2-g sample at 380°C for five minutes in advance and then keeping this sample at this temperature under a load of 0.7 MPa using a flow tester of Shimadzu Corp. and a 2φ-8L die in conformity with ASTM D1238.
Both the high molecular weight polytetrafluoroethylene and the low molecular weight polytetrafluoroethylene are preferably in the form of powder.
The production method preferably further includes (3) heating the high molecular weight polytetrafluoroethylene up to a temperature that is not lower than the primary melting point thereof to provide a molded article before the step (1), the molded article having a specific gravity of 1.0 g/cm³ or higher.
The disclosure also relates to powder containing low molecular weight polytetrafluoroethylene, the low molecular weight polytetrafluoroethylene having a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s and containing 30 or more carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain, the powder containing perfluorooctanoic acid and salts thereof in a total amount of not less than 5 ppb but less than 20 ppb.

- Advantageous Effects of Invention

The disclosure can provide a method for producing low molecular weight polytetrafluoroethylene less likely to generate C6-C14 perfluorocarboxylic acids and salts thereof.

DESCRIPTION OF EMBODIMENTS

The disclosure will be specifically described hereinbelow.
Irradiation of high molecular weight PTFE under conventional irradiation conditions provides not only low molecular weight PTFE having a higher melt viscosity than high molecular weight PTFE but also C6-C14 perfluorocarboxylic acids or salts thereof. These compounds contains non-naturally occurring, difficult-to-decompose substances which are further indicated to have high bioaccumulation, i.e., perfluorooctanoic acid containing 8 carbon atoms and salts thereof, perfluorononanoic acid containing 9 carbon atoms and salts thereof, and perfluorodecanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, and perfluorotetradecanoic acid respectively containing 10, 11, 12, 13, and 14 carbon atoms and salts thereof.
Irradiation of high molecular weight PTFE under conventional irradiation conditions may unfortunately generate 25 ppb or more of perfluorooctanoic acid containing 8 carbon atoms or salts thereof.
In the production method of the disclosure, irradiation of the high molecular weight PTFE in an atmosphere in which the oxygen concentration is controlled within a strictly limited range less likely to generate C6-C14 perfluorocarboxylic acids and salts thereof. Normally, irradiation in an atmosphere in which the oxygen concentration is low has difficulty in providing low molecular weight PTFE. In contrast, the production method of the disclosure enables easy production of low molecular weight PTFE.
In the production method of the disclosure, C6-C14 perfluorosulfonic acids and salts thereof are less likely to be generated.
The gas mixture contains an inert gas and oxygen. The inert gas needs to be a gas inert to a reaction of generating low molecular weight PTFE by irradiation. Examples of the inert gas include gases containing nitrogen, helium, or argon. Preferred are gases containing nitrogen.
The gas mixture has an oxygen content relative to the total of the inert gas and oxygen of 1 to 5 vol%. When the oxygen content of the gas mixture is within the above range, low molecular weight PTFE is easily obtained by irradiation of the high molecular weight PTFE in the step (2), while C6-C14 perfluorocarboxylic acids and salts thereof are less likely to be generated. The oxygen content of the gas mixture is preferably 2 vol% or more, more preferably 2.5 vol% or more.
The airtight container herein means a container which can be sealed up so as to adjust the oxygen concentration in the airtight container. Thus, the airtight container may be coupled with pipes for intake and exhaust of the gas mixture and for exhausting gas inside the airtight container, and may be coupled with components such as pipes, caps, valves, and flanges which are closed during irradiation. The airtight container may have any shape, such as a cylindrical shape, a prismatic shape, or a spherical shape, or may be a bag with a variable capacity. The container may be formed of any material, such as metal, glass, or a polymer. The material and structure of the airtight container need to be radiolucent and not deteriorated by irradiation. The airtight container needs not to be a pressure-resistant container.
The substances may be fed into the airtight container by, for example, a method in which the high molecular weight PTFE is placed in the airtight container, and then the airtight container is filled with the gas mixture.
In the step (2), the high molecular weight PTFE is irradiated by the following method. The step (2) is performed after the step (1).
The radiation is selected from electron beams, gamma rays, X-rays, and neutron beams. Electron beams or gamma rays are preferred.
The radiation preferably has an exposure dose of 1 to 2500 kGy, more preferably 1000 kGy or lower, still more preferably 750 kGy or lower, while more preferably 10 kGy or higher, still more preferably 50 kGy or higher.
The irradiation temperature may be any temperature within the range of 5°C to the melting point of high molecular weight PTFE. It is known that the molecular chain of high molecular weight PTFE is crosslinked around the melting point thereof. The irradiation temperature is therefore preferably 320°C or lower, more preferably 300°C or lower, still more preferably 260°C or lower, in order to provide low molecular weight PTFE. From an economic viewpoint, the irradiation is preferably performed at room temperature.
The production method of the disclosure may further include (3) heating the high molecular weight PTFE up to a temperature that is not lower than the primary melting point thereof to provide a molded article before the step (1). In this case, the molded article obtained in the step (3) can be used as the high molecular weight PTFE in the step (1).
The primary melting point is preferably 300°C or higher, more preferably 310°C or higher, still more preferably 320°C or higher.
The primary melting point means the maximum peak temperature on an endothermic curve present on the crystal melting curve when unsintered high molecular weight PTFE is analyzed with a differential scanning calorimeter. The endothermic curve is obtainable by increasing the temperature at a temperature-increasing rate of 10°C/min using a differential scanning calorimeter.
The molded article in the step (3) preferably has a specific gravity of 1.0 g/cm³ or higher, more preferably 1.5 g/cm³ or higher, while preferably 2.5 g/cm³ or lower. When the specific gravity of the molded article is within the above range, pores or irregularities on the surface are reduced, resulting in production of low molecular weight PTFE having a small specific surface area.
The specific gravity can be determined by water displacement.
The production method of the disclosure may further include pulverizing the molded article to provide powder of the high molecular weight PTFE after the step (3). The molded article may be first coarsely and then finely pulverized.
The production method of the disclosure may further include pulverizing the low molecular weight PTFE to provide a low molecular weight PTFE powder after the step (2).
The pulverization may be performed by any method, such as pulverization using a pulverizer. Examples of the pulverizer include impact-type pulverizers such as hammer mills, pin mills, and jet mills, and grinding-type pulverizers utilizing shearing force generated by unevenness between a rotary blade and a peripheral stator, such as cutter mills.
The pulverization temperature is preferably not lower than -200°C but lower than 50°C. In the case of freeze pulverization, the pulverization temperature is usually -200°C to -100°C. Still, the pulverization may be performed around room temperature (10°C to 30°C). Freeze pulverization is usually achieved by the use of liquid nitrogen, but such pulverization requires enormous equipment and high pulverization cost. In order to simplify the step and reduce the pulverization cost, the pulverization temperature is more preferably not lower than 10°C but lower than 50°C, still more preferably 10°C to 40°C, particularly preferably 10°C to 30°C.
The pulverization may be followed by removal of fine particles and fibrous particles by air classification, and further followed by removal of coarse particles by classification.
In the air classification, the pulverized particles are sent to a cylindrical classification chamber by decompressed air and dispersed by swirl flow inside the chamber, and fine particles are classified by centrifugal force. The fine particles are collected from the central portion into a cyclone and a bag filter. Inside the classification chamber is provided a rotary device such as a circular-cone-like cone or rotor configured to achieve homogeneous gyrating movement of the pulverized particles and the air.
In the case of using a classification cone, the classification point is adjusted by controlling the volume of the secondary air or the gap between the guide cone and the classification cone. In the case of using a rotor, the air volume inside the classification chamber is adjusted by the number of rotations of the rotor.
Examples of the method of removing coarse particles include air classification, vibration sieving, and ultrasonic sieving with meshes. Air classification is preferred.
Next, high molecular weight PTFE to be irradiated in the step (2) of the production method of the disclosure and low molecular weight PTFE to be obtained after the irradiation are described hereinbelow.
The low molecular weight PTFE has a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s. The term "low molecular weight" herein means that the melt viscosity is within the above range.
The melt viscosity is preferably 1.5 × 10³ Pa·s or higher, while preferably 3.0 × 10⁵ Pa·s or lower, more preferably 1.0 × 10⁵ Pa·s or lower.
The melt viscosity is a value determined by heating a 2-g sample at 380°C for five minutes in advance and then keeping this sample at this temperature under a load of 0.7 MPa using a flow tester (Shimadzu Corp.) and a 2φ-8L die in conformity with ASTM D1238.
The high molecular weight PTFE to be irradiated has a standard specific gravity (SSG) of 2.130 to 2.230. The standard specific gravity (SSG) is a value determined in conformity with ASTM D4895.
The high molecular weight PTFE has a significantly higher melt viscosity than the low molecular weight PTFE, and thus the melt viscosity thereof is difficult to measure accurately. In contrast, the melt viscosity of the low molecular weight PTFE is measurable, but the low molecular weight PTFE has difficulty in providing a molded article usable for measurement of standard specific gravity. Thus, the standard specific gravity thereof is difficult to measure accurately. Therefore, in the disclosure, the standard specific gravity is used as an indicator of the molecular weight of the high molecular weight PTFE to be irradiated, while the melt viscosity is used as an indicator of the molecular weight of the low molecular weight PTFE. For both the high molecular weight PTFE and the low molecular weight PTFE, no method for determining the molecular weight directly has been known so far.
The low molecular weight PTFE has a melting point of 320°C to 340°C, more preferably 324°C to 336°C.
The melting point is defined using a differential scanning calorimeter (DSC) as follows. Specifically, temperature calibration is performed in advance with indium and lead as standard samples. Then, about 3 mg of low molecular weight PTFE is put into an aluminum pan (crimped container), and the temperature is increased at a rate of 10°/min within the temperature range of 250°C to 380°C under air flow at 200 ml/min. The minimum point of the heat of fusion within this region is defined as the melting point.
In the production method of the disclosure, the high molecular weight PTFE may be in any form, such as powder, a molded article of the high molecular weight PTFE, or shavings generated by cutting the molded article of the high molecular weight PTFE. The high molecular weight PTFE in the form of powder can easily provide powder of the low molecular weight PTFE.
The low molecular weight PTFE obtainable by the production method of the disclosure may be in any form, and is preferably in the form of powder.
When the low molecular weight PTFE obtainable by the production method of the disclosure is in the form of powder, the specific surface area thereof is preferably 0.5 to 20 m²/g.
For the low molecular weight PTFE powder, both of the following two types are demanded, i.e., a small specific surface area type having a specific surface area of not smaller than 0.5 m²/g but smaller than 7.0 m²/g and a large specific surface area type having a specific surface area of not smaller than 7.0 m²/g and not larger than 20 m²/g.
The low molecular weight PTFE powder of a small specific surface area type has an advantage of easy dispersion in a matrix material such as coating. In contrast, such powder disperses in a matrix material with a large dispersed particle size, i.e., with poor fine dispersibility.
The low molecular weight PTFE powder of a small specific surface area type preferably has a specific surface area of 1.0 m²/g or larger, while preferably 5.0 m²/g or smaller, more preferably 3.0 m²/g or smaller. Suitable examples of the matrix material include plastics and inks, as well as coatings.
The low molecular weight PTFE powder of a large specific surface area type, when dispersed in a matrix material such as coating, has advantages of high surface-modifying effects, such as a small dispersed particle size in a matrix material and improved texture of the film surface, and a large amount of oil absorption. In contrast, such powder may not be easily dispersed in a matrix material (e.g., take a long time for dispersion), and may cause an increased viscosity of coating, for example.
The low molecular weight PTFE powder of a large specific surface area type preferably has a specific surface area of 8.0 m²/g or larger, while preferably 25 m²/g or smaller, more preferably 20 m²/g or smaller. Suitable examples of the matrix material include oils, greases, and coatings, as well as plastics.
The specific surface area is determined by the BET method using a surface analyzer (trade name: BELSORP-mini II, MicrotracBEL Corp.), a gas mixture of 30% nitrogen and 70% helium as carrier gas, and liquid nitrogen for cooling.
When the low molecular weight PTFE obtainable by the production method of the disclosure is in the form of powder, the average particle size thereof is preferably 0.5 to 200 um, more preferably 50 um or smaller, still more preferably 25 um or smaller, particularly preferably 10 um or smaller. As mentioned here, powder having a relatively small average particle size, when used as an additive for coating, for example, can provide a film having much better surface smoothness.
The average particle size is equivalent to the particle size corresponding to 50% of the cumulative volume in the particle size distribution determined using a laser diffraction particle size distribution analyzer (HELOS & RODOS) available from Jeol Ltd. at a dispersive pressure of 3.0 bar without cascade impaction.
The production method of the disclosure can provide low molecular weight PTFE containing less C6-C14 perfluorocarboxylic acids and salts thereof after the step (2) . The low molecular weight PTFE obtainable by the production method of the disclosure preferably contains C6-C14 perfluorocarboxylic acids and salts thereof in a total amount by mass of not more than 50 ppb, more preferably less than 25 ppb, still more preferably not more than 20 ppb, still further preferably not more than 15 ppb, particularly preferably not more than 10 ppb. The lower limit of the amount may be lower than the detection limit. Preferably, the lower limit is 5 ppb.
The amount of the perfluorocarboxylic acids and salts thereof can be determined by liquid chromatography.
The low molecular weight PTFE obtainable by the production method of the disclosure is also characterized in that it contains less perfluorooctanoic acid and salts thereof. The low molecular weight PTFE obtainable by the production method of the disclosure preferably contains perfluorooctanoic acid and salts thereof in a total amount by mass of less than 25 ppb, more preferably not more than 20 ppb, still more preferably not more than 15 ppb, particularly preferably not more than 10 ppb. The lower limit may be lower than the detection limit. Preferably, the lower limit is 5 ppb.
The amount of perfluorooctanoic acid and salts thereof can be determined by liquid chromatography.
The low molecular weight PTFE obtainable by the production method of the disclosure is also characterized in that it contains less C6-C14 perfluorosulfonic acids and salts thereof. The low molecular weight PTFE obtainable by the production method of the disclosure preferably contains C6-C14 perfluorosulfonic acids and salts thereof in a total amount by mass of less than 25 ppb, more preferably not more than 20 ppb, still more preferably not more than 15 ppb, particularly preferably not more than 10 ppb. The lower limit thereof may be lower than the detection limit. Preferably, the lower limit is 5 ppb.
The amount of the perfluorosulfonic acids and salts thereof is determined by liquid chromatography, as described below.
The low molecular weight PTFE preferably contains 30 or more carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain. The number of carboxyl groups is more preferably 35 or more per 10⁶ carbon atoms in the main chain. The upper limit of the number of carboxyl groups may be any value, and is preferably 500, more preferably 350, still more preferably 65, per 10⁶ carbon atoms in the main chain, for example. The carboxyl groups may be generated at ends of the molecular chain of the low molecular weight PTFE by the irradiation of the high molecular weight PTFE in the presence of oxygen, for example. The number of carboxyl groups after irradiation increases in accordance with the amount of modification in the high molecular weight PTFE. As the low molecular weight PTFE contains 30 or more carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain, it can have excellent dispersibility in molding materials, inks, cosmetics, coatings, greases, components for office automation devices, toner-modifying additives, additives for plating solutions. For example, micro powder is blended into hydrocarbon-based matrix resins, inks, and coatings for the purpose of improving the slidability, reducing the abrasion loss, preventing squeal, and improving the water and oil repellency. However, such micro powder, which is a perfluororesin, is originally poor in compatibility with matrix resins, inks, and coatings, and thus is difficult to disperse uniformly. In contrast, micro powder produced by irradiating and decomposing high molecular weight PTFE generates perfluorooctanoic acid (PFOA) and salts thereof and carboxyl groups as by-products due to the production method thereof. Carboxyl groups present at ends and other positions in the resulting micro powder consequently act as dispersants for hydrocarbon-based matrix resin, inks, and coatings.
The low molecular weight PTFE may contain, at ends of the molecular chain, unstable end groups derived from the chemical structure of a polymerization initiator or chain-transfer agent used in the polymerization reaction of the high molecular weight PTFE. Examples of the unstable end groups include, but are not limited to, -CH₂OH, -COOH, and -COOCH₃.
The low molecular weight PTFE may undergo stabilization of the unstable end groups. The unstable end groups may be stabilized by any method, such as a method of exposing the unstable end groups to fluorine-containing gas to convert them into trifluoromethyl groups (-CF₃), for example.
The low molecular weight PTFE may contain amidated ends. The end amidation may be performed by any method, such as a method of bringing fluorocarbonyl groups (-COF) obtained by exposure to fluorine-containing gas into contact with ammonia gas as disclosed in JP H04-20507 A , for example.
The low molecular weight PTFE with stabilization or end amidation of the unstable end groups as described above can be well compatible with opposite materials and have improved dispersibility when used as an additive for opposite materials such as coatings, greases, cosmetics, plating solutions, toners, and plastics.
The PTFE may be a homo-PTFE consisting only of a tetrafluoroethylene (TFE) unit or may be a modified PTFE containing a TFE unit and a modifying monomer unit based on a modifying monomer copolymerizable with TFE. In the production method of the disclosure, the composition of the polymer is not changed. Thus, the low molecular weight PTFE has the composition of the high molecular weight PTFE as it is.
In the modified PTFE, the proportion of the modifying monomer unit is preferably 0.001 to 1% by mass, more preferably 0.01% by mass or more, while more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, of all the monomer units. The term "modifying monomer unit" herein means a moiety that is part of the molecular structure of the modified PTFE and is derived from a modifying monomer. The term "all the monomer units" herein means all the moieties derived from monomers in the molecular structure of the modified PTFE. The proportion of the modifying monomer unit can be determined by any known method such as Fourier transform infrared spectroscopy (FT-IR).
The modifying monomer may be any one copolymerizable with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene (HFP); chlorofluoroolefins such as chlorotrifluoroethylene (CTFE); hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride (VDF); perfluorovinyl ether; perfluoroalkylethylenes; and ethylene. One modifying monomer may be used, or multiple modifying monomers may be used.
Examples of the perfluorovinyl ether include, but are not limited to, unsaturated perfluoro compounds represented by the following formula (1):

CF₂=CF-ORf (1)

wherein Rf is a perfluoroorganic group. The "perfluoroorganic group" herein means an organic group in which all the hydrogen atoms bonded to any carbon atom are replaced by fluorine atoms. The perfluoroorganic group may contain ether oxygen.
Examples of the perfluorovinyl ether include perfluoro(alkyl vinyl ethers) (PAVEs) represented by the formula (1) in which Rf is a C1-C10 perfluoroalkyl group. The perfluoroalkyl group preferably contains 1 to 5 carbon atoms.
Examples of the perfluoroalkyl group in the PAVE include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, and perfluorohexyl groups. Preferred is perfluoro (propyl vinyl ether) (PPVE) in which the perfluoroalkyl group is a perfluoropropyl group.
Examples of the perfluorovinyl ether also include those represented by the formula (1) in which Rf is a C4-C9 perfluoro(alkoxyalkyl) group, those represented by the formula (1) in which Rf is a group represented by the following formula:

(wherein m is 0 or an integer of 1 to 4), and those represented by the formula (1) in which Rf is a group represented by the following formula:
wherein n is an integer of 1 to 4.
Examples of the perfluoroalkylethylenes include, but are not limited to, (perfluorobutyl)ethylene (PFBE), (perfluorohexyl)ethylene, and (perfluorooctyl)ethylene.
The modifying monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VDF, PPVE, PFBE, and ethylene. It is more preferably at least one selected from the group consisting of HFP and CTFE.
The disclosure also relates to powder containing low molecular weight polytetrafluoroethylene, the low molecular weight polytetrafluoroethylene having a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s and containing 30 or more carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain, the powder containing perfluorooctanoic acid and salts thereof in a total amount of 5 -20 ppb. The total amount is on a mass basis. The total amount is more preferably not more than 15 ppb, particularly preferably not more than 10 ppb.
The powder of the disclosure contains C6-C14 perfluorocarboxylic acids and salts thereof in a total amount by mass of 5 ppb or more and 50 ppb or less, more preferably less than 25 ppb, still more preferably not more than 20 ppb, still further preferably not more than 15 ppb, particularly preferably not more than 10 ppb.
The powder of the disclosure contains C6-C14 perfluorosulfonic acids and salts thereof in a total amount by mass of not less than 5 ppb but less than 25 ppb, more preferably not more than 20 ppb, still more preferably not more than 15 ppb, particularly preferably not more than 10 ppb.
The powder of the disclosure has a specific surface area of preferably 0.5 to 20 m²/g. The specific surface area is more preferably 7.0 m²/g or more.
The powder of the disclosure has an average particle size of 0.5 to 200 µm.
For the low molecular weight PTFE constituting the powder of the disclosure, the composition, melt viscosity, and specifications of carboxyl groups at ends of the molecular chain are similar to those described for the low molecular weight PTFE obtainable by the production method of the disclosure.
The low molecular weight PTFE constituting the powder of the disclosure may contain unstable end groups at ends of the molecule chain, and these unstable end groups may be stabilized, end-amidated, or fluorinated. These embodiments are also similar to those described for the low molecular weight PTFE obtainable by the production method of the disclosure.
The powder of the disclosure may be obtainable by producing powdery low molecular weight PTFE by the aforementioned production method of the disclosure.
The low molecular weight PTFE and the powder can suitably be used as molding materials, inks, cosmetics, coatings, greases, components for office automation devices, additives for modifying toners, organic photoconductor materials for copiers, and additives for plating solutions, for example. Examples of the molding materials include engineering plastics such as polyoxybenzoyl polyester, polyimide, polyamide, polyamide-imide, polyacetal, polycarbonate, and polyphenylene sulfide. The low molecular weight PTFE is particularly suitable as a thickening agent for greases.
The low molecular weight PTFE and the powder can suitably be used as additives for molding materials for improving the non-adhesiveness and slidability of rollers of copiers, for improving the texture of molded articles of engineering plastics, such as surface sheets of furniture, dashboards of automobiles, and covers of home appliances, and for improving the smoothness and abrasion resistance of machine elements generating mechanical friction, such as light-load bearings, gears, cams, buttons of push-button telephones, movie projectors, camera components, and sliding materials, for example.
The low molecular weight PTFE and the powder can be used as additives for coatings for the purpose of improving the smoothness of varnish and paint. The low molecular weight PTFE and the powder can be used as additives for cosmetics for the purpose of improving the smoothness of cosmetics such as foundation.
The low molecular weight PTFE and the powder can also be suitably used for improving the oil or water repellency of wax and for improving the smoothness of greases and toners.
The low molecular weight PTFE and the powder can be used as electrode binders of secondary batteries and fuel cells, hardness adjusters for electrode binders, and water repellents for electrode surfaces.
The low molecular weight PTFE or the powder may be combined with a lubricant to provide grease. The grease is characterized by containing the low molecular weight PTFE or the powder and a lubricant. Thus, the low molecular weight PTFE or the powder is uniformly and stably dispersed in the lubricant and the grease exhibits excellent performance such as load resistance, electric insulation, and low moisture absorption.
The lubricant (base oil) may be either mineral oil or synthetic oil. Examples of the lubricant (base oil) include paraffinic or naphthenic mineral oils, and synthetic oils such as synthetic hydrocarbon oils, ester oils, fluorine oils, and silicone oils. In terms of heat resistance, fluorine oils are preferred. Examples of the fluorine oils include perfluoropolyether oil and polychlorotrifluoroethylene with a low polymerization degree. The polychlorotrifluoroethylene with a low polymerization degree may have a weight average molecular weight of 500 to 1200.
The grease may further contain a thickening agent. Examples of the thickening agent include metal soaps, composite metal soaps, bentonite, phthalocyanin, silica gel, urea compounds, urea/urethane compounds, urethane compounds, and imide compounds. Examples of the metal soaps include sodium soap, calcium soap, aluminum soap, and lithium soap. Examples of the urea compounds, urea/urethane compounds, and urethane compounds include diurea compounds, triurea compounds, tetraurea compounds, other polyurea compounds, urea/urethane compounds, diurethane compounds, and mixtures thereof.
The grease contains the low molecular weight PTFE or the powder in an amount of preferably 0.1 to 60% by mass, more preferably 0.5% by mass or more, still more preferably 5% by mass or more, while more preferably 50% by mass or less. A grease containing too large an amount of the low molecular weight PTFE or powder may be too hard to provide sufficient lubrication. A grease containing too small an amount of the low molecular weight PTFE or powder may fail to exert the sealability.
The grease may also contain any of additives such as solid lubricants, extreme pressure agents, antioxidants, oilness agents, anticorrosives, viscosity index improvers, and detergent dispersants.

EXAMPLES

The disclosure is more specifically described below with reference to examples. Still, the disclosure is not intended to be limited to the following examples.
The parameters in the examples were determined by the following methods.

Melt viscosity

The melt viscosity was determined by heating a 2-g sample at 380°C for five minutes in advance and then keeping this sample at this temperature under a load of 0.7 MPa using a flow tester (Shimadzu Corp.) and a 2φ-8L die in conformity with ASTM D1238.

Number of carboxyl end groups

The following measurement was performed in conformity with the method of analyzing end groups disclosed in JP H04-20507 A .
Low molecular weight PTFE powder was preformed with a hand press to provide a film having a thickness of about 0.1 mm. The resulting film was subjected to infrared absorption spectrum analysis. PTFE with completely fluorinated ends by contact with fluorine gas was also subjected to infrared absorption spectrum analysis. Based on the difference spectrum therebetween, the number of carboxyl end groups was calculated by the following formula. $\begin{array}{l} Number of carboxyl end groups (per 10^{6} carbon atoms) = \\ (1 \times K) / t \end{array}$

l:: absorbance
K:: correction coefficient
t:: film thickness (mm)

The absorption frequency and correction coefficient of the carboxyl group are respectively set to 3560 cm^-1 and 440.

Amount of perfluorooctanoic acid and salts thereof (PFOA)

The amount of perfluorooctanoic acid and salts thereof was determined using a liquid chromatography-mass spectrometer (LC-MS ACQUITY UPLC/TQD, Waters) . Measurement powder (1 g) was mixed with acetonitrile (5 ml) and the mixture was sonicated for 60 minutes, so that perfluorooctanoic acid was extracted. The resulting liquid phase was analyzed by multiple reaction monitoring (MRM). Acetonitrile (A) and an aqueous ammonium acetate solution (20 mmol/L) (B) were passed at a predetermined concentration gradient (A/B = 40/60 for 2 min and 80/20 for 1 min) as mobile phases. A separation column (ACQUITY UPLC BEH C18 1.7 µm) was used at a column temperature of 40°C and an injection volume of 5 µL. Electrospray ionization (ESI) in a negative mode was used as the ionization method, and the cone voltage was set to 25 V. The ratio of the molecular weight of precursor ions to the molecular weight of product ions was measured to be 413/369. The amount of perfluorooctanoic acid and salts thereof was calculated by the external standard method. The detection limit of this measurement is 5 ppb.

Amount of C6-C14 perfluorocarboxylic acids and salts thereof (PFC)

C6-C14 perfluorocarboxylic acids and salts thereof were detected using a liquid chromatography-mass spectrometer (LC-MS ACQUITY UPLC/TQD, Waters). The solution used was the liquid phase extracted in the measurement of perfluorooctanoic acid, and the measurement was performed by MRM. The measurement conditions were based on the measurement conditions for perfluorooctanoic acid, but the concentration gradient was changed (A/B = 10/90 for 1.5 min and 90/10 for 3.5 min). The ratio of the molecular weight of precursor ions to the molecular weight of product ions was measured to be 313/269 for perfluorohexanoic acid (C6), 363/319 for perfluoroheptanoic acid (C7), 413/369 for perfluorooctanoic acid (C8), 463/419 for perfluorononanoic acid (C9), 513/469 for perfluorodecanoic acid (C10), 563/519 for perfluoroundecanoic acid (C11), 613/569 for perfluorododecanoic acid (C12), 663/619 for perfluorotridecanoic acid (C13), and 713/669 for perfluorotetradecanoic acid (C14).
The total amount of C6-C14 perfluorocarboxylic acids and salts thereof was calculated from the amount (X) of the perfluorooctanoic acid obtained in the above measurement by the following formula. The detection limit of this measurement is 5 ppb. $(A_{C 6} + A_{C 7} + A_{C 8} + A_{C 9} + A_{C 10} + A_{C 11} + A_{C 12} + A_{C 13} + A_{C 14}) / A_{C 8} \times X$

A_C6: peak area of perfluorohexanoic acid
A_C7: peak area of perfluoroheptanoic acid
A_C8: peak area of perfluorooctanoic acid
A_C9: peak area of perfluorononanoic acid
A_C10: peak area of perfluorodecanoic acid
A_C11: peak area of perfluoroundecanoic acid
A_C12: peak area of perfluorododecanoic acid
A_C13: peak area of perfluorotridecanoic acid
A_C14: peak area of perfluorotetradecanoic acid
X: amount of perfluorooctanoic acid calculated from the MRM measurement result by the external standard method

Average particle size

The average particle size was equivalent to the particle size corresponding to 50% of the cumulative volume in the particle size distribution determined using a laser diffraction particle size distribution analyzer (HELOS & RODOS) available from Jeol Ltd. at a dispersive pressure of 1.0 bar without cascade impaction.

Example 1

A barrier nylon bag was charged with 50 g of PTFE fine powder (standard specific gravity determined in conformity with ASTM D 4895: 2.175, concentrations of PFC and PFOA were lower than the detection limits) . The inside of the bag was purged with nitrogen gas 10 times, and then purged with a gas mixture (oxygen:nitrogen = 1: 99 (vol%)) 5 times, so that the atmosphere in the bag was made to be an atmosphere of the gas mixture. The bag was then heat-sealed.
The PTFE fine powder in the bag was irradiated with 200 kGy of cobalt-60 γ rays at room temperature. Thereby, a low molecular weight PTFE powder was obtained.
The physical properties of the resulting low molecular weight PTFE powder were determined. The results are shown in Table 1.

Examples 2 to 5 and Comparative Examples 1 to 4

Low molecular weight PTFE powders were obtained as in Example 1, except that the amount of the PTFE fine powder and the composition of the irradiation atmosphere were changed as shown in Table 1.

The physical properties of the obtained low molecular weight PTFE powders were determined in the same manner as in Example 1. The results are shown in Table 1.

[Table 1]

	PTFE fine powder (g)	Composition of irradiation atmosphere (vol%)		Irradiation dose	PFOA content (ppb)	PFC content (ppb)	Average particle size (µm)	Melt viscosity (Pa·s)	Carboxy group (pcs)
	PTFE fine powder (g)	Oxygen	Nitrogen	Irradiation dose	PFOA content (ppb)	PFC content (ppb)	Average particle size (µm)	Melt viscosity (Pa·s)	Carboxy group (pcs)
Example 1	50	1	99	200 kGy	8	12	66	8.6 × 10⁴	32
Example 2	60	2	98	200 kGy	7	10	70	8.8 × 10⁴	32
Example 3	50	2.5	97.5	200 kGy	11	17	60	7.0 × 10⁴	34
Example 4	50	5	95	200 kGy	15	24	52	5.3 × 10⁴	36
Example 5	120	5	95	200 kGy	12	17	67	6.3 × 10⁴	36
Comparative Example 1	60	10	90	200 kGy	22	38	38	3.8 × 10⁴	63
Comparative Example 2	60	16	84	200 kGy	51	112	31	3.0 × 10⁴	68
Comparative Example 3	60	19	81	200 kGy	75	155	33	1.8 × 10⁴	74
Comparative Example 4	60	21	79	200 kGy	85	181	30	1.3 × 10⁴	74

Claims

A method for producing low molecular weight polytetrafluoroethylene (PTFE), comprising:
(1) feeding high molecular weight PTFE having a standard specific gravity of 2.130-2.230, determined in conformity with ASTM D4895, and a gas mixture containing an inert gas and oxygen and having an oxygen content relative to the total of the inert gas and oxygen of 1-5 vol% into an airtight container and

(2) irradiating the high molecular weight PTFE with a radiation selected from electron beams, gamma rays, X-rays, and neutron beams to provide low molecular weight PTFE which has a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s, wherein the melt viscosity is a value determined by heating a 2-g sample at 380°C for five minutes in advance and then keeping this sample at this temperature under a load of 0.7 MPa using a flow tester of Shimadzu Corp. and a 2φ-8L die in conformity with ASTM D1238.
The method of claim 1, wherein both the high molecular weight PTFE and the low molecular weight PTFE are in the form of powder.
The method of claim 1 or 2, further comprising, before step (1), the step of
(3) heating the high molecular weight PTFE up to a temperature that is not lower than the primary melting point thereof to provide a molded article having a specific gravity of ≥ 1.0 g/cm³ as determined by water displacement,
wherein the primary melting point is defined as the maximum peak temperature on an endothermic curve present on the crystal melting curve when unsintered high molecular weight PTFE is analyzed with a differential scanning calorimeter; the endothermic curve being obtained by increasing the temperature at a temperature-increasing rate of 10°C/min using a differential scanning calorimeter.
Powder comprising low molecular weight PTFE having a melt viscosity at 380°C of 1.0 × 10² to 7.0 × 10⁵ Pa·s and containing ≥ 30 carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain, the powder containing perfluorooctanoic acid and salts thereof in a total amount of 5-20 ppb,
wherein the amount of perfluorooctanoic acid and salts thereof is determined by liquid chromatography using the method described in the specification; the melt viscosity is determined as set out in Claim 1, and the number of carboxyl groups at ends of the molecular chain per 10⁶ carbon atoms in the main chain is determined by infrared absorption spectrum analysis using the method described in the specification.